It is widely appreciated that electro-optic activity in polymer-dispersed liquid crystals (PDLCs) depends on separation of the polymer and liquid crystal (LC) phases. Since the phase structure develops in a non-equilibrium system, the morphology of the LC domains depends on the details of the chemical and physical processes active during domain formation. The nature of the interface between the polymer and liquid crystal phases is of particular interest. This work discusses the two-phase morphology in an acrylate-based system that develops during polymerization-induced phase separation (PIPS). Using small-angle X-ray scattering (SAXS) and ultra-small-angle X-ray scattering (USAXS), we find that interfaces in PDLCs developed from an acrylate-based recipe are more disordered than generally appreciated. Information gained from SAXS and USAXS is compared to data from scanning electron microscopy (SEM) and transmission electron microscopy (TEM). To elucidate the apparent discrepancies between imaging and scattering, we investigated the effects of SEM sample preparation. We observe significant alteration of the interface morphology due to the leaching of the LC phase. © 2005 Elsevier Ltd. All rights reserved.